技术领域technical field
本发明涉及一种粘结剂材料，具体地说是以碱蓬籽饼粕为主要原料的生物环保型粘结剂。The invention relates to a binder material, in particular to a bio-environmental protection binder with suaeda seed cake as the main raw material.
背景技术Background technique
粘结剂广泛应用于各个领域，如型煤粘结剂、球团粘结剂、胶合板粘结剂及固沙粘结剂等。目前应用最多的粘结剂是由高分子化学和石油化学制造的“合成粘结剂”。Binders are widely used in various fields, such as briquette binders, pellet binders, plywood binders and sand-fixing binders. The most widely used binders are "synthetic binders" produced by polymer chemistry and petrochemistry.
粘结剂在固沙领域主要是用在沙漠及土壤风蚀严重的地区，用于沙粒的粘结，目的在于形成固结层，防止风沙起尘。传统的固沙粘结剂可分为：水泥浆类、水玻璃类、石油产品类和高分子聚合物高吸水树脂类。这些固沙粘结剂能够使地表沙土得以固定，具有一定的稳定性和保水性，从而达到固定流沙和治理荒漠化土地的目的。但是有的材料成本高，有的材料不能为植物生长创造良好的水土环境，有的材料甚至会对环境造成污染。比如，石油产品类材料施用后难以降解，长期滞留于表层沙土中，造成环境二次污染。新型固沙粘结剂包括：对工农林业副产品进行改性处理的生态环境固沙材料、利用微生物技术的微生物固沙材料和有机-无机合成的复合固沙材料等几类。它们具有使用性能好、资源与能源消耗少、与生态环境相容性好等诸多优点。In the field of sand fixation, binders are mainly used in deserts and areas with severe wind erosion of the soil. They are used to bond sand particles. The purpose is to form a consolidated layer and prevent dust from wind and sand. Traditional sand-fixing binders can be divided into: cement slurry, water glass, petroleum products and polymer superabsorbent resin. These sand-fixing binders can fix the surface sand and have certain stability and water retention, so as to achieve the purpose of fixing quicksand and controlling desertification land. However, some materials are expensive, some materials cannot create a good water and soil environment for plant growth, and some materials may even pollute the environment. For example, petroleum product materials are difficult to degrade after application, and remain in the surface sand for a long time, causing secondary pollution to the environment. New sand-fixing binders include: ecological environment sand-fixing materials modified by industrial, agricultural and forestry by-products, microbial sand-fixing materials using microbial technology, and organic-inorganic composite sand-fixing materials. They have many advantages such as good performance, low resource and energy consumption, and good compatibility with the ecological environment.
粘结剂在胶合板领域通常采用的是脲醛树脂，受热容易产生游离甲醛，导致二次污染，这也是室内甲醛超标的主要原因。所以研制低含量甚至不含游离甲醛的粘结剂是当前主流的研究方向。Urea-formaldehyde resin is usually used as the adhesive in the field of plywood, and it is easy to generate free formaldehyde when heated, resulting in secondary pollution, which is also the main reason for indoor formaldehyde exceeding the standard. Therefore, the development of binders with low content or even no free formaldehyde is the current mainstream research direction.
粘结剂在纸箱粘结方面通常采用水玻璃粘结剂，水玻璃即硅酸钠在实际使用中出现泛碱、吸潮现象，使粘结物脱落，效果不好。所以采用环保型粘结剂作为替代品，有着广阔的前景。Adhesives usually use water glass adhesives in the bonding of cartons. Water glass, that is, sodium silicate, has pan-alkali and moisture absorption in actual use, causing the adhesive to fall off and the effect is not good. Therefore, the use of environmentally friendly adhesives as a substitute has broad prospects.
总之，高分子化学和石油化学制造的“合成粘结剂”，有的材料成本高，有的性能不佳，有的甚至对环境造成二次污染，危害人体健康。因此，研究既环保又便宜的粘结剂有着重要的现实意义。In short, some "synthetic binders" produced by polymer chemistry and petrochemistry have high material costs, some have poor performance, and some even cause secondary pollution to the environment and endanger human health. Therefore, it is of great practical significance to study environmentally friendly and cheap binders.
发明内容Contents of the invention
本发明的目的在于获得一种对生态友好的生物环保型粘结剂。The purpose of the present invention is to obtain an eco-friendly bio-environmental protection adhesive.
本发明的另一个目的在于提供一种生物环保型粘结剂的制备方法。Another object of the present invention is to provide a preparation method of bio-environmental protection adhesive.
本发明的第一个方面，提供了一种生物环保型粘结剂，所述粘结剂主要包括碱蓬籽饼粕、表面活性剂、增稠剂及粘合剂；以总重量为100份计，所述粘结剂各主要组分的重量份数为：The first aspect of the present invention provides a kind of bio-environmental protection type binder, and described binder mainly comprises Suaeda salsa seed cake, surfactant, thickener and adhesive; With total weight being 100 parts In total, the parts by weight of each main component of the binder are:
碱蓬籽饼粕 1.2-4.0份；Suaeda seed cake 1.2-4.0 parts;
表面活性剂 0.4-1.0份；Surfactant 0.4-1.0 parts;
增稠剂 0.8-3.0份；Thickener 0.8-3.0 parts;
粘合剂 0.5-1.5份；Adhesive 0.5-1.5 parts;
防腐剂 1.0-1.5份；Preservatives 1.0-1.5 parts;
其余为水。The rest is water.
在一个优选实施例中，所述碱蓬为盐地碱蓬、翅碱蓬、角碱蓬、硬枝碱蓬中的一种或多种。In a preferred embodiment, the Suaeda salsa is one or more of Suaeda salsa, Suaeda pterygium, Suaeda salsa, and Suaeda hardbrachia.
在一个优选实施例中，所述碱蓬籽饼粕为碱蓬籽经压榨榨油处理或溶剂浸提后得到的尾料。使用时需破碎、研细、过筛，得到粒径小于0.125mm的碱蓬籽饼粉。In a preferred embodiment, the Suaeda salsa seed cake is the tailings obtained after the Suaeda salsa seeds are subjected to oil pressing or solvent extraction. When used, it needs to be crushed, ground and sieved to obtain Suaeda salsa seed cake powder with a particle size of less than 0.125mm.
在一个优选实施例中，所述表面活性剂为十二烷基苯磺酸钠，其结构为直链结构，即LAS。In a preferred embodiment, the surfactant is sodium dodecylbenzenesulfonate, which has a linear structure, namely LAS.
在一个优选实施例中，所述增稠剂为羧甲基纤维素钠，由天然纤维素与苛性碱及一氯醋酸反应后制得的一种阴离子型高分子化合物，分子量为6400(±1000)，密度为0.5-0.7g/cm3。In a preferred embodiment, the thickener is sodium carboxymethyl cellulose, a kind of anionic macromolecule compound prepared by reacting natural cellulose with caustic alkali and monochloroacetic acid, with a molecular weight of 6400 (± 1000 ), the density is 0.5-0.7g/cm3 .
在一个优选实施例中，所述粘合剂为聚乙烯醇17-88、聚乙烯醇17-92及聚乙烯醇17-99中的一种或多种。In a preferred embodiment, the binder is one or more of polyvinyl alcohol 17-88, polyvinyl alcohol 17-92 and polyvinyl alcohol 17-99.
在一个优选实施例中，所述防腐剂为山梨酸钾、苯甲酸及其盐中的一种或多种。In a preferred embodiment, the preservative is one or more of potassium sorbate, benzoic acid and salts thereof.
在一个优选实施例中，制得的所述生物环保型粘结剂粘度为40-1500厘泊。In a preferred embodiment, the prepared bio-environmentally friendly adhesive has a viscosity of 40-1500 centipoise.
本发明的另一个方面，提供了一种制备生物环保型粘结剂的方法，包括如下步骤：Another aspect of the present invention provides a method for preparing a bio-environmental friendly adhesive, comprising the steps of:
a)将所述碱蓬籽饼粕破碎研磨至细粉，过筛，取粒径小于0.125mm的碱蓬籽饼粉；a) Crushing and grinding the Suaeda salsa seed cake to fine powder, sieving, and taking the Suaeda salsa seed cake powder with a particle size less than 0.125mm;
b)将步骤a)得到的碱蓬籽饼粉置于沸水中做热处理，蒸煮30min；然后取下静置，降温至65-75℃之间；b) Put the Suaeda salsa seed cake powder obtained in step a) into boiling water for heat treatment, and cook for 30 minutes; then take it out and let it stand, and cool it down to 65-75°C;
c)在不断搅拌的情况下，将羧甲基纤维素钠缓慢均匀地撒到烧杯内，使羧甲基纤维素钠完全溶解，备用；在不断搅拌的情况下，将聚乙烯醇缓缓加入20℃左右的冷水中充分溶胀、分散，而后升温到95-100℃加速溶解，直到溶液不再含有微小颗粒，再经过60目不锈钢筛过滤杂质后，即可备用；c) In the case of constant stirring, slowly and evenly sprinkle sodium carboxymethyl cellulose into the beaker to completely dissolve the sodium carboxymethyl cellulose, and set aside; in the case of constant stirring, slowly add polyvinyl alcohol Fully swell and disperse in cold water at around 20°C, then heat up to 95-100°C to accelerate dissolution until the solution no longer contains tiny particles, and then pass through a 60-mesh stainless steel sieve to filter impurities before use;
d)在1000r/min的搅拌速度下，先在步骤b)得到的碱蓬籽饼粉溶液中缓慢加入十二烷基苯磺酸钠和聚乙烯醇溶液，搅拌10min，再缓慢加入羧甲基纤维素钠溶液，搅拌20min；然后，调整搅拌速度为200r/min，继续搅拌60min，整个反应过程温度控制在65-75℃之间；d) At a stirring speed of 1000r/min, slowly add sodium dodecylbenzenesulfonate and polyvinyl alcohol solution to the Suaeda salsa seed cake powder solution obtained in step b), stir for 10min, and then slowly add carboxymethyl Sodium cellulose solution, stirred for 20 minutes; then, adjust the stirring speed to 200r/min, continue stirring for 60 minutes, and control the temperature during the whole reaction process between 65-75°C;
e)取下静置，降温至室温后，加入所述防腐剂，搅拌5min，即得所述生物环保型粘结剂。与其他粘结剂相比本发明具有以下优点：e) Take it off and let it stand, and after cooling down to room temperature, add the preservative and stir for 5 minutes to obtain the bio-environmental-friendly adhesive. Compared with other adhesives, the present invention has the following advantages:
(1)本发明所采用碱蓬籽饼粕来源于植物的种子，属于农业副产品。采用碱蓬籽饼粕作为合成粘结剂的主要原料，可以解决碱蓬籽饼粕的处置问题，实现碱蓬籽饼粕这一庞大的农副产品资源的再利用价值，减少工业化工原料的使用量，使成本大大降低。(1) The Suaeda salsa seed cake used in the present invention is derived from the seeds of plants and belongs to agricultural by-products. Using Suaeda salsa seed cake as the main raw material for synthetic binder can solve the disposal problem of Suaeda salsa seed cake, realize the reuse value of Suaeda salsa seed cake, a huge agricultural and sideline product resource, and reduce the use of industrial chemical raw materials quantity, the cost is greatly reduced.
(2)本发明以碱蓬籽饼粕作为主要原材料，无毒无害，绿色环保。用于农田土壤固沙，具有良好的固沙作用，保护期过后又可被土壤微生物降解，与土壤生态环境相容性好，不会对农田土壤造成危害；因其含有丰富的有机质，还会为农作物提供生物质养料及少量钙磷等营养元素。(2) The present invention uses Suaeda salsa seed cake as the main raw material, which is non-toxic, harmless, and environmentally friendly. Used for sand fixation in farmland soil, it has a good sand fixation effect, and can be degraded by soil microorganisms after the protection period, has good compatibility with the soil ecological environment, and will not cause harm to farmland soil; because it is rich in organic matter, it can also be used for crops. Provide biomass nutrients and a small amount of nutrients such as calcium and phosphorus.
(3)本发明所述生物环保型粘结剂，还可作为粘结纸箱、纸张及胶合板等的粘合剂。(3) The bio-environmental protection adhesive of the present invention can also be used as an adhesive for bonding cartons, paper and plywood.
(4)本发明所述制备方法，工艺简单且易于操作，节省了设备、能源及人力投入的成本。(4) The preparation method of the present invention has a simple process and is easy to operate, saving the cost of equipment, energy and human input.
具体实施方式Detailed ways
实施例1Example 1
将盐地碱蓬籽饼破碎，然后研磨至细粉，过120目筛，取盐地碱蓬籽饼粉6.0g，置于500ml沸水中，蒸煮30min，然后降温至65-75℃之间。Crush the Suaeda salsa seed cake, then grind it to a fine powder, pass through a 120-mesh sieve, take 6.0 g of the Suaeda salsa seed cake powder, put it in 500 ml of boiling water, cook for 30 minutes, and then cool down to 65-75 °C.
称量4.0g十二烷基苯磺酸钠，备用；在烧杯中盛取100ml的水，置于恒温磁力搅拌器上，称量3.0g羧甲基纤维素钠，在不断搅拌的情况下，将羧甲基纤维素钠缓慢均匀地撒到烧杯内，使羧甲基纤维素钠完全溶解，备用。Weigh 4.0g sodium dodecylbenzene sulfonate, standby; Fill the water of 100ml in the beaker, place on the constant temperature magnetic stirrer, weigh 3.0g sodium carboxymethylcellulose, under the situation of constant stirring, Sprinkle the sodium carboxymethylcellulose into the beaker slowly and evenly to dissolve the sodium carboxymethylcellulose completely and set aside.
将温度在65-75℃之间的盐地碱蓬籽饼粉溶液放在恒温磁力搅拌器上，在1000r/min的搅拌速度下，先缓慢加入十二烷基苯磺酸钠，再缓慢加入羧甲基纤维素钠溶液，快速搅拌20min；然后，调整搅拌速度为200r/min，继续搅拌70min，整个反应过程温度控制在65-75℃之间。Put the Suaeda salsa seed cake powder solution with a temperature between 65-75°C on a constant temperature magnetic stirrer, and at a stirring speed of 1000r/min, first slowly add sodium dodecylbenzenesulfonate, and then slowly add The sodium carboxymethyl cellulose solution was stirred rapidly for 20 minutes; then, the stirring speed was adjusted to 200 r/min, and the stirring was continued for 70 minutes, and the temperature of the whole reaction process was controlled between 65-75°C.
取下静置，降至室温后，加入山梨酸钾5.0g，搅拌5min，即得产品。Take it off and let it stand, and after cooling down to room temperature, add 5.0 g of potassium sorbate and stir for 5 minutes to obtain the product.
本实施例制备得到生物环保型粘结剂的性能测试结果见表1。Table 1 shows the performance test results of the bio-environmentally friendly adhesive prepared in this example.
实施例2Example 2
将盐地碱蓬籽饼破碎，然后研磨至细粉，过120目筛，取盐地碱蓬籽饼粉10.0g，置于400ml沸水中，蒸煮30min，然后降温至65-75℃之间。Crush the Suaeda salsa seed cake, then grind it to a fine powder, pass through a 120-mesh sieve, take 10.0 g of the Suaeda salsa seed cake powder, put it in 400 ml of boiling water, cook for 30 minutes, and then cool down to 65-75 °C.
称量4.0g十二烷基苯磺酸钠，备用；在烧杯中盛取100ml的水，置于恒温磁力搅拌器上，称量8.0g羧甲基纤维素钠，在不断搅拌的情况下，将羧甲基纤维素钠缓慢均匀地撒到烧杯内，使羧甲基纤维素钠完全溶解，备用；另取一个烧杯，盛取100ml的水，称量4.0g聚乙烯醇，边搅拌边将本品缓缓加入20℃左右的冷水中充分溶胀、分散，而后升温到95-100℃加速溶解，直到溶液不再含有微小颗粒，再经过60目不锈钢筛过滤杂质后，即可备用。Weigh 4.0g sodium dodecylbenzene sulfonate, standby; Fill the water of 100ml in the beaker, place on the constant temperature magnetic stirrer, weigh 8.0g sodium carboxymethylcellulose, under the situation of constant stirring, Sprinkle sodium carboxymethylcellulose into the beaker slowly and evenly to completely dissolve the sodium carboxymethylcellulose, and set aside; take another beaker, fill it with 100ml of water, weigh 4.0g of polyvinyl alcohol, and mix it while stirring Slowly add this product to cold water at about 20°C to fully swell and disperse, then heat up to 95-100°C to accelerate dissolution until the solution no longer contains tiny particles, and then filter impurities through a 60-mesh stainless steel sieve before use.
将温度在65-75℃之间的盐地碱蓬籽饼粉溶液放在恒温磁力搅拌器上，在1000r/min的搅拌速度下，先缓慢加入十二烷基苯磺酸钠和聚乙烯醇溶液，搅拌10min，再缓慢加入羧甲基纤维素钠溶液，搅拌20min；然后，调整搅拌速度为200r/min，继续搅拌60min，整个反应过程温度控制在65-75℃之间。Put the Suaeda salsa seed cake powder solution at a temperature between 65-75°C on a constant temperature magnetic stirrer, and slowly add sodium dodecylbenzenesulfonate and polyvinyl alcohol at a stirring speed of 1000r/min Solution, stirred for 10 minutes, then slowly added sodium carboxymethylcellulose solution, stirred for 20 minutes; then, adjusted the stirring speed to 200r/min, continued to stir for 60 minutes, and the temperature of the whole reaction process was controlled between 65-75°C.
取下静置，降至室温后，加入苯甲酸钠5.0g，搅拌5min，即得产品。Take it down and let it stand, and after cooling down to room temperature, add 5.0 g of sodium benzoate and stir for 5 minutes to obtain the product.
本实施例制备得到生物环保型粘结剂的性能测试结果见表1。Table 1 shows the performance test results of the bio-environmentally friendly adhesive prepared in this example.
实施例3Example 3
本实施例中，生物环保型粘结剂的制备步骤与实施例1相同，仅对制备生物环保型粘结剂所需原料的配比进行变化。In this example, the preparation steps of the bio-environmental-friendly binder are the same as in Example 1, only the ratio of the raw materials required for the preparation of the bio-environmental-friendly binder is changed.
制备过程中所需的各原料组成及配比分别如下：(g)Each raw material composition and proportioning required in the preparation process are as follows respectively: (g)
盐也碱蓬籽饼粉 6.0；Suaeda seed cake powder 6.0;
十二烷基苯磺酸钠 3.0；Sodium dodecylbenzenesulfonate 3.0;
羧甲基纤维素钠 10.0；Sodium carboxymethyl cellulose 10.0;
山梨酸钾 5.0；Potassium sorbate 5.0;
清水 600.0。Clear water 600.0.
本实施例制备得到生物环保型粘结剂的性能测试结果见表1。Table 1 shows the performance test results of the bio-environmentally friendly adhesive prepared in this example.
实施例4Example 4
本实施例中，生物环保型粘结剂的制备步骤与实施例1相同，仅对制备生物环保型粘结剂所需原料的配比进行变化。In this example, the preparation steps of the bio-environmental-friendly binder are the same as in Example 1, only the ratio of the raw materials required for the preparation of the bio-environmental-friendly binder is changed.
制备过程中所需的各原料组成及配比分别如下：(g)Each raw material composition and proportioning required in the preparation process are as follows respectively: (g)
盐地碱蓬籽饼粉 8.0；Suaeda salsa seed cake powder 8.0;
十二烷基苯磺酸钠 4.0；Sodium dodecylbenzenesulfonate 4.0;
羧甲基纤维素钠 10.0；Sodium carboxymethyl cellulose 10.0;
山梨酸钾 4.0；Potassium sorbate 4.0;
清水 600.0。Clear water 600.0.
本实施例制备得到生物环保型粘结剂的性能测试结果见表1。Table 1 shows the performance test results of the bio-environmentally friendly adhesive prepared in this example.
实施例5Example 5
本实施例中，生物环保型粘结剂的制备步骤与实施例2相同，仅对制备环无保型粘结剂所需原料的配比进行变化。In this example, the preparation steps of the bio-environment-friendly adhesive are the same as in Example 2, only the ratio of the raw materials required for the preparation of the environmentally-friendly adhesive is changed.
制备过程中所需的各原料组成及配比分别如下：(g)Each raw material composition and proportioning required in the preparation process are as follows respectively: (g)
盐地碱蓬籽饼粉 10.0；Suaeda salsa seed cake powder 10.0;
十二烷基苯磺酸钠 4.0；Sodium dodecylbenzenesulfonate 4.0;
羧甲基纤维素钠 12.0；Sodium Carboxymethyl Cellulose 12.0;
聚乙烯醇 4.0；Polyvinyl alcohol 4.0;
苯甲酸钠 4.0；Sodium Benzoate 4.0;
清水 600.0。Clear water 600.0.
本实施例制备得到生物环保型粘结剂的性能测试结果见表1。Table 1 shows the performance test results of the bio-environmentally friendly adhesive prepared in this example.
对实施例1-5中制备得到的生物环保型粘结剂进行粘度及粘结强度测试。其中粘度采用旋转粘度计测量；粘结强度以土模所能承受的抗压强度来表示，采用无侧限压力仪测量。测试环境，温度为20℃。测试结果见表1。Viscosity and bond strength tests were performed on the bio-environmentally friendly adhesives prepared in Examples 1-5. The viscosity is measured by a rotational viscometer; the bond strength is expressed by the compressive strength that the soil mold can withstand, and is measured by an unconfined pressure instrument. The test environment, the temperature is 20°C. The test results are shown in Table 1.
表1Table 1
土模的制备：将生物环保型粘结剂与粒径小于0.125mm的土壤颗粒按照1∶7的比例掺和均匀，装入Φ50×60的圆柱形模具中，制成土模，置于鼓风干燥器中在35℃条件下干燥24小时，取出，将干燥的圆柱形土模上下两个表面均打磨平整且相互平行，使之在测试时受力均匀。Preparation of the soil mold: Mix the bio-environmental-friendly binder and the soil particles with a particle size of less than 0.125mm evenly at a ratio of 1:7, put them into a Φ50×60 cylindrical mold to make a soil mold, and place it in a drum Dry in an air dryer at 35°C for 24 hours, take it out, and polish the upper and lower surfaces of the dried cylindrical soil mold to be flat and parallel to each other, so that it is evenly stressed during the test.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110385656CN102504757B (en) | 2011-11-29 | 2011-11-29 | Biological environment-friendly adhesion agent and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110385656CN102504757B (en) | 2011-11-29 | 2011-11-29 | Biological environment-friendly adhesion agent and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN102504757A CN102504757A (en) | 2012-06-20 |
| CN102504757Btrue CN102504757B (en) | 2013-05-01 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110385656Expired - Fee RelatedCN102504757B (en) | 2011-11-29 | 2011-11-29 | Biological environment-friendly adhesion agent and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN102504757B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863965A (en)* | 2012-10-15 | 2013-01-09 | 南开大学 | Eco-friendly sand stabilization dust depressor and preparation method thereof |
| CN103710066A (en)* | 2013-12-20 | 2014-04-09 | 广西柳州浚业科技有限公司 | Composite binder for industrial briquette and preparation method thereof |
| CN104178625B (en)* | 2014-08-21 | 2016-08-24 | 东北大学 | A kind of magnesite powder pelletizing preparation method preventing from bursting in smelting process |
| CN107033828A (en)* | 2017-05-23 | 2017-08-11 | 林玉萍 | A kind of water-based glue |
| CN107057794A (en)* | 2017-05-26 | 2017-08-18 | 桂林聚能环保科技有限责任公司 | A kind of house refuse modification forming and the method for gasification |
| CN109749685A (en)* | 2017-11-08 | 2019-05-14 | 丹阳市易通安全技术服务有限公司 | A kind of glued board adhesive composition and its preparation process |
| CN108384556B (en)* | 2018-04-09 | 2021-07-02 | 孙美玲 | Preparation method of degradable sand fixing agent |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948416A (en)* | 2006-10-20 | 2007-04-18 | 南昌大学 | New technology of perparing formaldehyde less wood adhesion agent using vegetable raw material rich in protein |
| CN101475790A (en)* | 2008-01-04 | 2009-07-08 | 杨光 | Novel timber adhesive and preparation thereof |
| CN101629019A (en)* | 2009-01-21 | 2010-01-20 | 郑州佰沃生物质材料有限公司 | Basic biomass synthetic resin and preparation method and application thereof |
| CN101875835A (en)* | 2009-11-27 | 2010-11-03 | 青岛生物能源与过程研究所 | Preparation method for formaldehyde-free protein adhesive |
| CN102146292A (en)* | 2010-12-22 | 2011-08-10 | 北京林丰源生态科技有限公司 | Vegetable gelatin adhesive for spray seeding and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948416A (en)* | 2006-10-20 | 2007-04-18 | 南昌大学 | New technology of perparing formaldehyde less wood adhesion agent using vegetable raw material rich in protein |
| CN101475790A (en)* | 2008-01-04 | 2009-07-08 | 杨光 | Novel timber adhesive and preparation thereof |
| CN101629019A (en)* | 2009-01-21 | 2010-01-20 | 郑州佰沃生物质材料有限公司 | Basic biomass synthetic resin and preparation method and application thereof |
| CN101875835A (en)* | 2009-11-27 | 2010-11-03 | 青岛生物能源与过程研究所 | Preparation method for formaldehyde-free protein adhesive |
| CN102146292A (en)* | 2010-12-22 | 2011-08-10 | 北京林丰源生态科技有限公司 | Vegetable gelatin adhesive for spray seeding and preparation method thereof |
| Publication number | Publication date |
|---|---|
| CN102504757A (en) | 2012-06-20 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102504757B (en) | Biological environment-friendly adhesion agent and preparation method thereof | |
| CN104186058B (en) | A kind of prone soil modification method | |
| CN103204745B (en) | Production process of urea formaldehyde humic acid organic fertilizer | |
| CN104449578B (en) | A kind of environmental-friendly dust suppressant and preparation method thereof | |
| CN101723765A (en) | Compound water retention soil conditioner and preparation thereof | |
| CN102863965A (en) | Eco-friendly sand stabilization dust depressor and preparation method thereof | |
| CN104876679A (en) | Coarse biochar slow-release fertilizer and preparation method thereof | |
| CN107325502A (en) | A kind of water conservation getting fat Biodegradable agricultural mulch film and preparation method thereof | |
| CN104140823B (en) | A kind of ground membrane preparation method using soil as film | |
| CN103360168A (en) | Preparation method of biological sand-solidification water-retention repairing agent | |
| CN102838995B (en) | Environment-friendly composite water retention agent, preparation and using method thereof | |
| CN104817413A (en) | Environment-friendly water-soil conserving soil modifier formula | |
| CN108383946A (en) | A kind of preparation of water-soluble environment protective sand-consolidating agent and application process | |
| CN104557345B (en) | Preparation method of hydrogel for nitrogenous fertilizer | |
| CN101463247B (en) | Composite type soil water retention agent and preparation | |
| CN106635043A (en) | Soil structure conditioner used for shajiang black soil and soil improving method | |
| CN104448165A (en) | Preparation method of farm-oriented nutrient water retaining agent using bagasse as raw material | |
| CN105036994B (en) | A kind of method for preparing rice light soil-less seedling raising ground substance using biological chelating technology | |
| CN103351217A (en) | Preparation method of multifunctional biomass carbon potash fertilizer | |
| CN110591647B (en) | Dust suppressant and preparation method and application thereof | |
| CN103274859A (en) | Humic acid synergistic high-tower compound fertilizer and production method thereof | |
| CN104876681A (en) | Fertilizer combining organic carbon and inorganic nutrients and preparation method of fertilizer | |
| CN114316996B (en) | Composite curing agent and preparation method thereof | |
| CN102212337A (en) | Coal dust inhibitor and production method thereof | |
| CN107520939B (en) | Oil-tea camellia husks flour additive agent and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20130501 Termination date:20151129 | |
| EXPY | Termination of patent right or utility model |